Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
  • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
  • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
  • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2321/00—Characterised by the use of unspecified rubbers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2738—Coating or impregnation intended to function as an adhesive to solid surfaces subsequently associated therewith
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
  • Y10T442/2893—Coated or impregnated polyamide fiber fabric
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2926—Coated or impregnated inorganic fiber fabric
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2926—Coated or impregnated inorganic fiber fabric
  • Y10T442/2984—Coated or impregnated carbon or carbonaceous fiber fabric

Definitions

• the invention relates to a composite consisting of a thermoplastic or thermo­setting polymer or a vulcanized or non-vulcanized rubber containing yarns, cords and/or fabrics provided with an adhesive.
• Polymeric or rubber composites in which yarns, cords and/or fabrics of synthetic polymers or regenerated cellulose are incorporated are well known. The strength and also several other physical properties of such composites have been found to be greatly improved over those of polymers or rubber in which no reinforcing materials are incorporated. It is further known that no full justice is done to these improved proper­ties unless there is a strong bond between the reinforcing material and the polymers or rubber in which this material is incorporated.
• the level of ad­hesion appears still to be unsatisfactory.
• the above problems are entirely or largely overcome by the present inven­tion, which provides a composite consisting of thermoplastic or thermoset­ting polymer or a vulcanized or non-vulcanized rubber containing yarns, cords and/or fabrics provided with an adhesive.
• the invention consists in that with a composite having the known composition mentioned in the opening paragraph the adhesive is a polyester-ester urethane built up of polyester-­ester units which are linked together by low molecular weight structural units of the formula wherein R1 represents a polyfunctional organic group having not more than 30 carbon atoms, and p is an integer of 2 or 3, which polyester units are com­posed of two types of polyester-ester units which are each built up of blocks comprising
• thermoplastic elastomers described in US Patent Specification 4 483 970.
• part of the thermoplastic elastomers described in it which are said to be excellently suitable to be injection moulded or extruded into shaped articles, could be used sur­prisingly successfully in composites for the purpose of enhancing the ad­hesion of yarns, cords and/or fabrics to the matrix material employed.
• the matrix of the composite may consist of a thermosetting or a thermoplastic synthetic material.
• suitable thermosetting synthetic materials for use within the scope of the present invention may be mentioned epoxy resins, unsaturated polyester resins and phenol formaldehyde resins.
• suitable thermoplastic synthetic materials include: polyethylene terephthalate and polybutylene terephthalate (PETP and PBTP), polyether-ether ketone (PEEK), polyether sulphone (PES), polyether imide (PEI), polymide (PI), polyhexamethylene adipamide (nylon 66), poly- ⁇ -caprolactam (Nylon 6), poly- ⁇ -dodecanecarboxylic acid (Nylon 12), or polycarbonate (PC).
• thermoplastic elastomers as described in US Patent Specification 3 023 192 and 3 763 109 and the polyester-ester urethanes according to US Patent Specification 4 483 970.
• polyester-ester urethanes according to the last-mentioned patent specification, there is no need to employ a separate adhesive.
• a vulcanized or non-vulcanized rubber is to be understood both a synthetic and a natural rubber.
• synthetic rubbers may be mentioned polybutadiene, polyisoprene, polybutadiene-styrene, polybutadiene acrylonitrile, polyisobutylene and polyacrylonitrile butadiene-styrene (ABS) rubber.
• the yarn and/or cords used for reinforcing the present composites are generally in the form of a fabric. However, they also may be used in the form of a knitted fabric, a braid or a non-woven fabric.
• a favourable em­bodiment consists in that a number of substantially parallel yarns are formed into a reinforcing layer with the adhesive according to the inven­tion. In this way a for instance 2 to 5 cm wide unidirectional tape or U.D. tape may be obtained which may be used for making shaped objects by the winding technique known in itself, with the matrix material being placed between the layers of reinforcing tape.
• U.D. tapes may be made to a width of up to 60 cm. These are applied in the hand lay up art, i.e.
• the yarns, cords and/or fabrics that form part of the composites according to the present invention may be made from the most widely varying materials. These include metal and carbon and inorganic and organic synthetic materials. In view of satisfactory adhesion, however, it is preferred that use should be made of yarns of synthetic materials based on organic polymers such as polyethylene terephthalate (PETP), polycaprolactam, nylon 66, and particularly aromatic polyamide.
• PETP polyethylene terephthalate
• nylon 66 polycaprolactam
• aromatic polyamide particularly aromatic polyamide.
• Aromatic polyamides are polyamides that consist entirely or substantially of recurring units of the general formula wherein A1, A2 and A3 represent the same or different divalent, one or more aromatic rings containing-rigid radicals, which may also contain a hetero­cyclic ring, of which radicals the chain extending bonds are in the para position to each other or are parallel and oppositely directed.
• these radicals include 1,4-phenylene, 4,4'-biphenylene, 1,5-­naphthalene and 2,6-naphthalene. They may contain substituents or not, e.g. halogen atoms or alkyl groups.
• the chain molecules of the aromatic polyamides may optionally contain up to 50 mole % of other groups, such as m-phenylene groups, non-rigid groups, such as alkyl groups, or ether, urea or ester groups such as 3,4'-diaminodiphenyl ether groups.
• the yarn according to the invention entirely or sub­stantially consists of poly-p-phenylene terephthalamide.
• Composite materials having optimum properties are obtained if according to the invention use is made of aromatic polyamide yarns having a modulus of elasticity of 60 to 140 GPa, an elongation at rupture of 2-4,5%, and a tensile strength of 2,5 to 3,5 GPa.
• the modulus of elasticity, the elongation at rupture and the tensile strength are measured in accordance with ASTM-D885. It has been found that an adhesive having satisfactory properties is generally obtained when the proportion of low-molecular weight structural units of the formula calculated as diphenylmethane-4,4'-diisocyanate (MDI) and based on the polyester-ester urethane is in the range of 0,5 to 12,5% by weight. Preference is given to an adhesive in which the proportion of low-molecular weight structural units of the formula is in the range of 1 to 10% by weight.
• MDI diphenylmethane-4,4'-diisocyanate
• At least 80 mole % of the low molecular weight diol and at least 80 mole % of the low molecular weight dicarboxylic acid from which the ester units of the formula are derived is formed respectively of 1,4-butanediol and terephthalic acid.
• diols with 2-15, and particularly 5-10 carbon atoms such as ethylene, propylene, isobutylene, pentamethylene, 2,2-dimethyltri­methylene, hexamethylene, and decamethylene glycol, dihydroxy cyclohexane, dimethanol cyclohexane, resorcinol, hydroquinone and 1,5-dihydroxy naph­thalene.
• aliphatic diols containing 2-8 carbon atoms.
• Suitable dicarboxylic acids (other than terephthalic acid) having a mole­cular weight not exceeding 300 are aliphatic, cycloaliphatic or aromatic dicarboxylic acids.
• aliphatic dicarboxylic acids as used in the description of the invention refers to carboxylic acids having two carboxyl groups which are each attached to a saturated carbon atom. If the carbon atom to which the carboxyl group is attached is saturated and is in a ring, the acid is cycloaliphatic.
• Aromatic di­carboxylic acids are dicarboxylic acids having two carboxyl groups attached to carbon atoms in an isolated or fused ben­zene ring. It is not necessary that both functional carboxyl groups be at­tached to the same aromatic ring and where more than one ring is present, they can be joined by aliphatic or aromatic divalent radicals such as -O-or -SO2-.
• Representative aliphatic and cycloaliphatic acids which can be used for this invention are sebacic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, adipic acid, glutaric acid, succinic acid, carbonic acid, oxalic acid, azelaic acid, diethyl-malonic acid, allyl-­malonic acid, 4-cyclohexene-1,2-dicarboxylic acid, ⁇ , ⁇ '- ⁇ , ⁇ '-tetramethyl-­succinic acid, cyclopentanedicarboxylic acid, decahydro-1,5-naphthalene dicarboxylic acid, 4,4'-bicyclohexyl dicarboxylic acid, decahydro-2,6-­naphthalene dicarboxylic acid, 4,4'-methylene-bis-(cyclohexane carboxylic acid), 3,4-furan dicarboxylic acid
• Preferred aliphatic and cycloaliphatic acids are cyclohexane-dicarboxylic acids and adipic acid.
• Representative aromatic dicarboxylic acids which can be used include phthalic and isophthalic acids, bibenzoic acids, substituted dicarboxy com­pounds with two benzene nuclei such as bis(p-carboxyphenyl)ethane, p-oxy-­(p-carboxyphenyl)benzoic acid, ethylene-bis(p-oxybenzoic acid), 1,5-naph­thalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naph­thalene dicarboxylic acid, phenanthrene dicarboxylic acid, anthracene di­carboxylic acid, 4,4'-sulfonyl dibenzoic acid, and C1-C12 alkyl and/or ring substitution derivatives thereof, such as halo,
• Hydroxyl acids such as p( ⁇ -hydroxyethoxy)benzoic acid can also be used, providing an aromatic dicarboxylic acid is also present.
• Aromatic dicar­boxylic acids are a preferred class for preparing the ester units of the formula: Among the aromatic acids, those with 8-16 carbon atoms are preferred, particularly the phenylene dicarboxylic acids, i.e., phthalic and iso­phthalic acids. In view of the melting point and the relatively high crystallization or curing rate of the polyester-ester urethane it is preferred that the ester units of the formula should entirely or substantially be derived from polybutylene terephthalate.
• the procedure for preparing the low melting polyesters or polyester amides is known per se and similar to that used for preparing high melting poly­esters. It may be realized for instance by polycondensation of polyfunc­tional, preferably bifunctional alcohols, amino alcohols, hydroxycarboxylic acids, lactones, aminocarboxylic acids, cyclic carbonates or polycarboxylic acids. By a proper choice of the mixing ratio of the above-mentioned com­ponents any desirable molecular weight and number and type of terminal groups may be obtained.
• glycols such as 1,3- or 1,4-cyclohexanediol or 1,3- or 1,4-bis(hydroxymethyl)cyclohexane
• amino alcohols such as amino ethanol or amino propanol
• the low melting components also may entirely or partly be composed of lactones such as substituted or unsubstituted capro­lactone or butyrolactone. Under some circumstances, for instance to in­crease the melt viscosity of the endproduct, it may be recommended to in­corporate some small amount of higher functional compounds.
• lactones such as substituted or unsubstituted capro­lactone or butyrolactone.
• trimethylol ethane trimethylol propane or hexane triol.
• the low melting bifunctional components may also be derived from the following acids: glutaric acid, pimelic acid, suberic acid, iso­sebacic acid or ricinoleic acid. Also aliphatic dicarboxylic acids having hetero atoms, such as thiodipropionic acid may be used in the low melting bifunctional compounds. In addition there still may be mentioned cycloali­phatic dicarboxylic acids such as 1,3- or 1,4-cyclohexane dicarboxylic acid and terephthalic acid and isophthalic acid. For an essentially better resistance to hydrolysis preference is given to polyesters of which the constituents each consist of at least 5 carbon atoms.
• adipic acid and 2,2-dimethyl propanediol or mixtures of 1,6-­hexanediol and 2,2-dimethyl propanediol or 2-methyl-1,6-hexanediol may be mentioned.
• some other low melting bifunctional compounds may to a limited extent be incorporated into the segmented thermoplastic elastomers according to the invention.
• polyalkylene glycol ethers having terminal hydroxyl groups as obtained by reaction with water, diamines, di- or tri-­functional alcohols or amino alcohols.
• poly­tetrahydrofuran obtained by polymerization of tetrahydrofuran in the presence of acid catalysts or copolymers thereof with small amounts of ethylene oxide and/or propylene oxide.
• acid catalysts or copolymers thereof with small amounts of ethylene oxide and/or propylene oxide.
• ester units that may form a bifunctional polyester or polyester amide having a melting point not higher than 100°C are entirely or substantially derived from poly­caprolactone.
• the low molecular weight structural units of the formula which may be used according to the invention are derived from di- and tri­isocyanates.
• the diisocyanates may be represented by the general formula OCNRNCO, wherein R represents a divalent, aliphatic, alicyclic or aromatic group.
• diisocyanates of the aliphatic type examples include: hexamethylene diisocyanate, dimethyl hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, metaxylylene diisocyanate, paraxylylene diisocyanate, tetra­methylene diisocyanate.
• R represents an aromatic group, it may be sub­stituted for instance with a halogen, a lower alkyl or a lower alkoxy group.
• diisocyanates examples include:1-chloro-2,4-phenylene di­isocyanate, 2,4-toluene diisocyanate, a mixture of 2,4-toluene and 2,6-­toluene diisocyanate, tetramethylphenylene diisocyanate, diphenylmethane-­4,4'-diisocyanate, metaphenylene diisocyanate, paraphenylene diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, biphenylmethane-­4,4'-diisocyanate, biphenyldimethylmethane-4,4'-diisocyanate, benzophenone-­4,4'-diisocyanate, biphenylether diisocyanate and biphenylsulphide diiso­cyanate, 3,3'-dimethyldiphenyl-4,
• diisocyanates having an alicyclic group examples include isophoron diisocyanate, dicyclohexylmethane diisocyanate and 1,4-cyclo­hexane diisocyanate. It has been found that optimum properties are generally obtained if the ratio of the number of -NCO groups of the diisocyanate to the number of functional groups of the block polyester-esters is in the range of 1,1 to 1,5. Both with a view to the properties of the end product and simplicity of preparation preference is given according to the inven­tion to polyester-esters having hydroxyl end groups.
• the invention also relates to processes for the preparation of a polyester-­ester urethane of the composition mentioned hereinbefore to be used as ad­hesive.
• One of these processes is characterized in that a bifunctional polyester having a molecular weight of at least 1000 and built up of ester units of the formula wherein both G and R2 have the same meaning as indicated before, is reacted, while in the molten phase, with a bifunctional polyester or poly­ester amide having a molecular weight of at least 1500 and a melting point not higher than 100°C, after which the resulting polyester-ester is reacted with a low molecular weight coupling agent of the formula R1 [N C O] p wherein R1 and p have the afore-indicated meaning, in an amount such that the ratio of the number of -NCO groups to the number of functional groups of the polyester-ester is at least 1,0 and not higher than 5, the trans­esterification catalyst present in one or in both polyesters or polyester-­amides being entirely or partly deactivated before and/or during the prepa­ration of the polyester-ester.
• the present process is advantageously star­ted from a low-melting bifunctional polyester or polyester amide having a molecular weight of 1500 to 2500 and a high-melting polyester of the formula having a molecular weight in the range of 10 000 to 25 000.
• Preference is given then to the use of a high-melting polyester which entirely or sub­stantially consists of polybutylene terephthalate having a molecular weight in the range of 15 000 to 19 000.
• a high-­melting polyester having a molecular weight in the range of 1500 to 3000 preference is given to its use in combination with a low-melting polyester or polyester amide having a molecular weight in the range of 10 000 to 20 000.
• a titanium catalyst or a calcium salt, a manganese salt and/or a zinc salt For the purpose of transesterification in the preparation of the polyester use is generally made of a titanium catalyst or a calcium salt, a manganese salt and/or a zinc salt. These salts may be deactivated by adding precipitating or complexing agents. Deactivation also may be carried out by applying a thermal treatment. It has been found, for instance, that when the catalyst used is zinc acetate, it may be deactivated by heating to a tempe­rature of at least 200°C. Favourable results are particularly found to be obtained when use is made of complexing phosphorus compounds, which are also suitable to be used as stabilizers in polyesters.
• R, R1, R2 and R3 represent an organic group they generally do not contain more than 30, and preferably not more than 18 carbon atoms. As examples may be men­tioned alkyl, cycloalkyl, carboalkoxy alkyl, aryl, aralkyl and aroxy alkyl.
• phosphorus compounds that are excellently suitable to be used for the present purpose may be mentioned: triphenyl phosphate, tri­phenyl phosphite, triethyl phosphite, tricyclohexyl phosphite, tri-2-ethyl­hexyl trithiophosphite, trieicosyl phosphite, tri-o-chlorophenyl phosphite, 2-carbomethoxyethyl dimethyl phosphonate, hydroxymethyl phosphonic acid, diphenyl phosphinic acid, carboxymethyl phosphonic acid, carbethoxymethyl phosphonic acid, carboxyethyl phosphonic acid, tris(triethylene glycol)-­phosphate and more particularly carbethoxymethyl diethyl phosphonate and tri-p-tert.
• R1 and R2 may be the same or different and represent a hydrogen atom or an alkyl, cycloalkyl, aralkyl or aryl group each having not more than 20 carbon atoms, or the group OR3, wherein R3 represents a metal or ammonium or the same group or the same atom as R1, irrespective of the meaning of R1.
• Suitable phosphorus compounds include the inorganic acids such as orthophosphoric acid, phosphorous acid or hypophosphorous acid; phosphinic acid such as methyl phosphinic acid, ethyl phosphinic acid, iso­butyl phosphinic acid, benzyl phosphinic acid, phenyl phosphinic acid, cyclohexyl phosphinic acid or 4-methylphenyl phosphinic acid; phosphonic acids such as methyl phosphonic acid, ethyl phosphonic acid, isopropyl phosphonic acid, isobutyl phosphonic acid, benzyl phosphonic acid, phenyl phosphonic acid, cyclohexyl phosphonic acid, or 4-methylphenyl phosphonic acid; the partial esters of said acids, more particularly the C1-20 alkyl, cycloalkyl, aryl or aralkyl esters, such as the methyl, ethyl, propy
• the phosphorus compound used for deactivation corresponds to at least 0,5 phosphorus atoms per metal atom of the trans­esterification catalyst.
• Favourable results are as a rule obtained when the amount of phosphorus compounds used for deactivation corresponds to 1 to 15 phosphorus atoms per metal atom, preference being given to using 1 to 5 phosphorus atoms per metal atom.
• polyesters and/or polyester amides prepared in the presence of a catalytic amount of a titanium catalyst.
• a titanium catalyst is not only its high reactivity, but especially the ease with which it can be deactivated.
• suitable titanium catalysts include esters of titanium acid and the neutralized products thereof, hydrogenated hexa-alkoxy titanates of magnesium, titanyl oxalates, titanium halides, hydrolysed products of titanium halides, titanium hydroxide and titanium oxide hydrate and potassium titanium fluoride (K2TiF6).
• alkyl titanates such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate or tetrabutyl titanate, the neutralized products there­of, the hydrogenated magnesium hexa-alkoxy titanates, such as hydrogenated magnesium hexabutoxy titanate Mg (HTi[OC4H9]6)2, titanyl oxalate, calcium titanyl oxalate, titanium tetrachloride, the reaction product of titanium tetrachloride and hexane diol and the reaction mixture of titanium tetra­chloride and water.
• Said titanium catalysts are used alone or in combi­nation with magnesium acetate or calcium acetate.
• Inorganic titanates such as lanthanum titanate, calcium acetate/antimony trioxide mixtures and lithium alkoxides and magnesium alkoxides are examples of other suitable catalysts.
• the amount in which they are to be incorporated generally ranges from 0,005 to 0,3% by weight, calculated on the components taking part in the reaction. For a man skilled in the art it will not be difficult to decide on the amount of catalyst to be used for a given system.
• the low-melting polyesters or polyester amides that may be used according to the invention are commercially available. Applicant has found that they contain no or hardly any transesterification promoting catalysts. There is therefore generally no need for these low-melting components to be deactivated.
• the high-melting components are generally prepared in the presence of a transesterification promoting catalyst.
• the de­activating compound is a phosphorus compound
• the results obtained are generally satisfactory if the phosphorus compound is incorporated into the high-melting polyester prior to the reaction process and the mixture is kept in the molten state for at least 5 minutes.
• polyester-esters to be used according to the invention are usually prepared at a temperature ranging between the melting point of the highest-­melting component and 290°C.
• An alternative procedure for obtaining a poly­ester-ester urethane according to the invention consists in that a bifunc­tional polyester having a molecular weight of at least 1000 and built up of ester units of the formula wherein both G and R2 have the same meaning as indicated before, is reacted, while in the molten phase, with a bifunctional polyester or poly­ester amide having a molecular weight of at least 1000 and a melting point not higher than 100°C, after which the resulting polyesterester is reacted with a low molecular weight coupling agent of the formula R1 [N C O] p ' wherein R1 and p have the afore-indicated meaning, in an amount such that the ratio of the number of -NCO groups to the number of functional groups of the polyester-ester is at least 1,0 and not higher than 5.
• the length of time the high-­melting and the low-melting polyester or polyester amide must react with each other to give an optimally transesterified block polyester-ester depends, in part, on the average hydroxyl number, the amount of trans­esterification catalyst and the composition of the polyesters used. A man skilled in the art will have no difficulry in choosing such conditions for a given reaction mixture as will lead to a polyester-ester urethane having optimum properties.
• the invention will be further described in the following examples. They are, however, not to be construed as limiting the scope of the invention. For the determination of the properties of the polymers prepared in these examples use was made of the following methods:
• the melting point Tm p in °C was determined with a Du Pont Thermal Analyzer.
• the hardness in Shore D was determined in conformity with ASTM-D1484.
• the filament bundle was pulled out of the polymer films on an Instron tensile tester (of the 2211 type) at a cross-­head speed of 50 mm per minute.
• the force required to this end is expressed in newton (N)/dtex 1000.
• the above fabrics were either laminated with a film of 200 ⁇ m of the com­posite material forming polyester urethane or, after impregnation with said last-mentioned material, laminated with a film of, respectively, poly­butylene terephthalate (PBTP), polyethylene terephthalate (PETP), poly­hexamethylene adipamide (nylon 6,6) or polyether imide.
• PBTP poly­butylene terephthalate
• PETP polyethylene terephthalate
• nylon 6 polyethylene terephthalate
• the peel strength is given in N/cm.
• Example I The experiment of Example I was repeated, but in such a way that 73 parts of molten PBTP (molecular weight 16 000) were intensively mixed with 27 parts of PBA (molecular weight 1850) over a period of 210 minutes at 240°C. After adding 3500 ppm of PEE mixing was continued for 20 minutes at 240°C. Sub­sequently, 5,5 parts of MDI per 100 parts of polyester were added and mixed for 45 minutes at 240°C.
• PBTP molecular weight 16 000
• PBA molecular weight 1850
• stirring was continued for 120 minutes at 240°C.
• 3000 ppm of PEE were added, after which per 100 parts of polyester 0,8 parts of MDI were introduced into the mixture.
• reaction time 45 minutes at 240°C the following properties were measured:
• PBTP molecular weight 16000
• PBA molecular weight 1850
• HDI hexamethylene diisocyanate
• the polymers were prepared as indicated in Example IX, except that the PBTP was deactivated with 625 ppm PEE instead of with 1250 ppm. The following properties were measured:

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